Chemical process



. from the prior lrt in Patented is... 12. is

zsorsvz I scar, rnocsss Ewing Arundale, Colonial and Louis A. Mikeska,

velopment ware ' I NoDi-awlng.

* The present statements to a method for ."the production oi halogenated fatty acid' esters "of unsaturated alcohols. These novelunsaturated esters are obtained bythe condensation of oleflnsor other unsaturated compounds with aldehydes in the presence of a'cids.'

More particularly, the invention is concerned with the reaction between a'mono-olefln i I suchas-trimethylethylene, an aldehyde such as formaldehyde, and a halogenated organic acid such as 'mono, di-, or trichloracetic acid to yield the halogenated fatty. acid ester of an unsaturated alcohol. J I

The reaction between oleflns, aldehydes, and

organic acids has been described in French Pat ent 717,712. According to the disclosure and alyst must be-u'sed to bring about the reaction.

' The product is .a glycol diacetate which is finally saponified to a glycol.

The reaction or olefins with formaldehyde and organic acids in the presence of anhydrous metallic halides to-lorm unsaturated esters has been I described in copending application Serial No.

302,122 filed October 31, 1939. p I I The-pr cess of the present invention differs that the halogenated or ganic acid acts as (l) a catalyst for the olefinaldehyde condensation reaction, (2) an esteriiicationreagent, and (3) an esterification catalyst. No mineral acid or metallic halide catalyst is necessary in this process.-

{ cyclohexene; unsaturated compounds such as unsaturated eth'ers or halides, as well as mixtures of olefinic and parafllnic hydrocarbons. I

The aldehydes used in carrying out the process of this invention may be formaldehyde, acetaldehyde,propionaldehyde, or any compound suchas polymers of aldehydes, e. g., paraiormaldehyde (trioxymetlrvlene) which will decompose to yield an aldehyde under the reaction conditions.- The acid employed in the condensation is any one of the fatty acid series in which at least one of the substituents on the a carbon atom is a halogen; other halogen substituents may be substituted in Compan,

halogenated i'atty claims of this patent, a strong mineral acid cataldehyde on a mol per "acid. Examples wash. The ester. is

- olefin and acid.

. urated alcohols or cracked to Standard 01] Doa corporation oi Dela- Application December 28, 1946. Serial No. 372,171 I V 18 Claims. (c1. see-sat) other positions along the aliphatic than of the of such acids aremono-, di-, or trichloracetic acid, etc. a

The reactants preferably employed in the procteas are tertiary oleiins, formaldehyde, and alpha chlorinated fatty aci I The reaction proceeds readily at room temperature, however, temperatures between lo and 40 C. maybe used. *At'the temperature of the reaction, most of the loweroleilns will exert a moderate to high vapor pressure. 'Ihereiore, in order to provide adequate contact between the reactants, the reaction shouldbe conducted with in a closed vessel capable of withstanding moderately high pressures. e reaction is fairly rapid and is complete within from 1 to-20. hours depending upon the reactivity of the olefin em.-

I ployed and the activity or the halogenated or ganic acid.- Tha land of th e reactionmay be readily determined where solid forms ofaldehydes are used, as it is indicated when-allot the solid I aldehyde is dissolved. It is desirable to use an I excess of both olefin and organic acid over the mol basis. This excess will range from 0.1 to 1 mo I I The general procedure ior carrying out the reaction is to place the reactants in a closed con- 7 tainer equipped with a stirrer for providingintimate contact. The reactants are maintained at substantially room temperature and stirred until the reaction is complete after which the reaction twice with water, the

mixture is washed once or I wer ester layer beingwithdrawnjafter'each drying agent such as sodium sulfate, and illtered. The solvent is removed by evaporation and the residue vacuum distilled to recover the.

unsaturated ester. Instead of water washing, the crude reaction product resulting from the con densation of the oleiln, aldehyde and acid may be purified by vacuum distillation directly where by the ester is The unsaturated esters I ance with the process of the present invention are heavier than and insoluble in water. They may be hydrolyzed to the to give dienes.

I acid, mono-; or di-, alpha chloro- Q propionic acid, monoor di-, alpha bromobutyrlc thentreated with a dilute I alkali solution or not more-than 1% concentra-: tion and then extracted with an ether such-as diethylether or di-isopropyl ether. Theether'ex i tract is water washed and then dried overs separated from any unreacted if produced in accordcorresponding unsat-' Y denser. 275 parts of olefinic'compound with 7 of the reaction.

' atom in the alpha position, products all the reaction.

unsaturated ester. Y

v 7. A process in accordance with claim in which the tertiary olefin contains a tertiary dou-f The .iollowing example is given for the pur- .pose of illustrating the invention:

60 parts 0! paraformaldehyde were placed in a reactor equipped with a stirrer and reflux congrade) were added thereto and stirred wherepasty liquid resulted. The mixture parts of trimethylethylene were slowly run in with intermittent cooling.

7 The temperature was maintained between 20 and 30 C. The paraiormaldehyde disappeared and a clear'solution resulted. The product was Ether was then then washed twice with water. added and the extract was treated with a dilute carbonate solution until neutral.- The extract was then water washed and dried over sodium sulfate after which the ether was removed by evaporation andthe product vacuum distilled: 'The malority o! the material boiled between 100? and 120 C. at 3 mm. pressure.

What is claimed is:

1. A process comprising the reaction' oi an a substance selected from the group consisting of aldehydes and compounds decomposing, under the conditions oi the reac.

- tion, to yield aldehydes and a halogenated fatty acid which contains at least one halogen atom in recovering the products the alpha position, and

2. The process according to claim 1 inwhich the olefinic compound is a tertiary olefin containing a tertiary doubly bonded carbon atom tov which a methyl group is attached. i 3. The process comprising the reaction of an olefinic compound with formaldehyde and a halogenated fatty acid which contains-at least ichloracetic acid (practical one halogen atom in the alpha position, and re covering the products of the reaction,

.4. The process comprising the reaction of a tertiary olefin which contains a tertiary doubly.

bonded carbon atom'to which a methyl group is i.

attached fatty acid which 5. The process of producing anunsaturated ester of an composing, under halogenated acid of the fatty acid series, andrecovering saturated ester.

6. The process with formaldehyde and a halogenated.

contains atleast one halogen;

and recovering the the unl of an unsaturatedester of an alpha halogenated acid of the fatty monochloracetic acid.

8. A-process accordingto claim 6 in which the tertiary olefin contains atertiary doubly bonded carbon atom to which a methyl group is attached.

9.-The process acid series which comprises condensing a tertiary olefin, formaldehyde and an alpha halo-.-

g'enated acid of the fatty acid series; and recovr ering the unsaturated ester.

1o. Aprocess accordingto claim-0 m which the doubly bonded .carbon'atom to which amethyl group is attertiary olefin contains a tertiary tached.

11. I'he process oi producing unsaturated 12. A process according claim. 11 in which the tertiary olefin contains a tertiary doubly. 1 bonded carbon atom to which a methyl group is attached and in which the chloracetic. acid is 13. A process'according the tertiary olefincontainsa tertiary doubly bonded carbon atom to which a methyl group'is attached and the chloracetic acid is dichlorac'etic acid V 14. A process. according to claim 11 in which the tertiary olefin contains. a tertiary doubly bonded carbon atom to which a methyl group is attached andthe chloracetic acid is trichloracetic acid. i

l5. 1he process 01 producing an unsaturated ester of dichloracetic acid which comprises condensing trimethylethylene; triozwmethylene and dichloracetic acid at a temperature between 10 and 40 C. and recoveringthe unsaturated ester;

16. Process of producing anunsaturated ester o1 chloracetic acid which comprises condensing 'trimethylethylene, trioxymethylene and (noble-- racetic acid with stirring, and'under pressure at alpha halogenated acidof the ram acid series which comprises condensing a tertiary oleiln, a substance selectedfrom the groupcom; of eldehydes and compounds readily de-,

theconditions of the reactiorn.

to yield aldehydes and an alpha least equal to the total vapor pressure of the reaction mixture "andat room temperature, washhe condensate'with-water, removing the water and any unreacted olefin and acid, solvent extracting. the washed condensate, removing the I solvent by evaporation and recovering the un- 1 gsaturatedester by I V '17. 'I'he process of producing an unsaturated ester otdichloracetic acid which comprises cona vacuum distillation.

' densing trimethylethylene, trioxymethylene and acid series which comprises condensing a tertiary oleiln, a substance selected from thegroup' con-' sisting of aldehydes andcompounds readilydecomposing, under the conditions of the reaction, alpha dihalogenated acid '0! the fatty acid series, and recovering the to yield aldehydes andan bly bonded carbon atom to which a methyl group is attached.

dichloracetic acid at substantially room temperature and recovering the unsaturated ester of dichloracetic acid by vacuum distillation under fractionation conditions.

18. As a composition of matter, the ester oi 2-methyl-butene-(1)-ol (4 and dichloracetic A navme ARUNnALE.

LOUIS A. mxasm of producing an unsaturated ester of an alpha halogenated acid or the fatty to claim 11 in which a 

